Isobornyl aryl ethers



Patented Jan. 8, 1952 Leland J'. Kitchen; Akron, hio assignor to The tFirestonfi'lire Rubber Company, "Akron;

. (Dhimazcorporation of Ohio No.DrawinglgApplication February 21 i948, f.ser ia1No.10,1s5

=min'e, iodine, fluorine; "alkoxy such as -;methoxy,

ethoxy, propoxy, isopropoxy, etcr; -ni'troso; phenyl, phenoxy andothersubstituted" phenols, etc. -Long-chain substituentsin' the-orthoposition present-steric hindrance so that if a phenol con- "taining "an'ortho a1-kyl substituent is employed ordinarily alky-l substituentscontaining no more than 4 or 5 carbonjat'omswill be used.-- I-Io'wever,the invention includes the ethers obtained from all alkyl-substitutedphenols,-regardless'oi ,the length of the side; chain andregardles'sof Ythe number of. substituents. Thu-s aside chain, if. in the meta orpara-position. mayhave up to .about 18 carbon atoms,.-such-as.pentadecyl.and octadecyl. Although ordinarily the etherswillbe derived. frommonocyclic .phenol,.the-invention includes ethers produced fromnaphthols, hydroquinone;; catechol,-- rand --resorcinol, bothsubstitutedand unsubstituted. f

The invention-relates. more particularly tosthe ethers obtained fromunsubstituted vcamphene and unsubstituted 'tricyclene, and unsubstitutedor alkyl-substituted phenols. Whether reacted with camphene ortricyclene theisobornyl ether of the corresponding phenol isobtained;High: yields are obtained if the reaction is carried out at lowtemperatures. I p

The phenols .Whichmay be used inflproducing .theethersinclude f "iPhenol 2-methyl145chloropheno] p-Cresol 4-flu0rq o-Cresol4-methoxyphenol 2,4-dimethylphenol 4.-nitr0phenol 2,6-dimethylpheno1Beta-.naphthol 4-ch1orophenol Hydroquinone 2,4-dichlorophenol Catechol4-bromophenol 4-tert+amylpheno1 I fl bromophenol -2-.ethoxyethoxyphenol4 -2,4-:dibromophenol t-iethylphenol F 6 Claims (01. 260-612 'I'heter-penes which may be used inproducing the .ethers include camphene andtricyclene.

' The following examples illustrate how the new compounds may be' made.The boronfluoride catalyst-referred to in the following examplesconsisted of 45 per cent ofboron trifluoriderin ether. i

EXAMPLE 1' i V IsobornykQ-hcnyletherj 272 grams of camphene was mixedWitt-141188 grams of phenol. To thexstirred mixture maintained at .atemperature between 1 and +15 C.

was added 6.5 grams of BF: (45 per cent solution ether). :In: 120 lminutes the reactionrwas 's Opped by addition (if-aqueous alkali.Distillation-'yieldedphenyl isobornylether, a water-white a'liquid' witha ,faint odor; whichwas-obtained in '82 per cent yield. Therisobornyl'phenyl ether had the following" properties: ,B. P. 151?, -C./10' mm.,167?. 'C./20 mm; ;295::C;/,744 -mm.; n =1.5265, ugh-1.5241, n *:15221;d4 9=l-.0.058; M '='-7'0.36 (calcd., 69.73).

EXAMPLE. 2

Isobomyl o-tolyl ether A mixture of 136 grams camphene and l22 gramso-cresol, stirred and cooled to 5 to 10 C. was treated with 2 :ml.ofiBFs-ether catalyst during thirty minutes. v A. few. minutes later themixture crystallized to a mushy solid. After an hour .the'solid wasshaken with NaOH solution and petroleum ether. ;The oil :layer,distilled, yielded isobornyl o-tolyl ether in 88 per cent yield.Thezproduct, a. colorless; liquid with a very slight *odor,.had B.P.-164.5. Cx/l-O mm; and n ?=,11-.5274 (supercooled :li'quid). itcrystallized when cooled. Recrystallized froms ac'etone, it had .M. P.

48.5'48.8 C. I v

Analysis: Calcd. for CHI-I240: C, 83.55%; H, 9.90%- Found: C,-83.73%;'H, 10.03%'.

v 220 grams of p-cresol was mixed with 214 -grams-of camphene and 9grams-of BF3 (45.-per cent :ether solution). :The reaction: mixture,.was keptgbelow 10 C. for-eleven days; A somewhat viscous liquid with alight-yellow tinge andza slight-odor wasotbtained in a yield of percent. The isobornyl p-tolylether had the following properties: B. P.164.5 0. .10 mm..;-..n .=l.519.0;

with stirring over a period of 90 minutes.

3 EXAMPLE4 Isobornyl 2,4-dimethylphenyl ether A solution of camphenedissolved in an equivalent amount of 2,4-dimethylphenol (Tech. gradewith a melting point of 18 to 20.5" C.) was treated with 2 per cent ofbenzene sulfonic acid (70 per cent) at a temperature of to C. andallowed to stand for several days. The yield was 95 to 98 per cent.Isobornyl 2,4-dimethyl-- phenyl ether has a boiling point of 154 C./3mm,

or 176 C./ mm. On recrystallization from 3:1 alcohol-acetone it had; amelting .point of 57.6-57.8 C.: 11. =1.5230 (super cooled liquid).

Analysis: Calcd. for C1aH2e0: C, 83.66%; H,

10.14%; M. W., 258.39. Found; 83.55%;v

10.42 M. W., 255 (micro-Bast).

EXAMPLE 5 Isobornyl 3,5-dimethylphenyl ether 136 grams of camphene and122 grams of 3,5- dimethylphenol were mixed with 3 grams of BFs (45 percent solution in ether) in 100 m1. toluene at 3 to +5 C. On completionof the reaction a yield of 84 per cent of isobornyl 3,5- dimethylphenylether was obtained from the reaction mixture. The product was acolorless liquid with a peculiar odor. Identifying characteristics werefound to be: B. P. 173.5 C/ 10 mm.;

78.96). EXAMPLE 6 Isobornyl p-methowylphenyl ether Equal molecularproportions of camphene and p -methoxyphenol were reacted with about 1per cent of BF: (45 per cent solution in ether) as catalyst. Thetemperature was not allowed to rise about 5 to 10 C. After one hundredforty- -five minutes the reaction mixture was worked up I in the mannerdescribed in the previous examples.

A yield of 85 per cent was obtained. The product is characterized by thefollowing: B. P. 183 C/10 mm.; n =1.5278; d4 =1.0388 (super cooled); M=77.l5 (Calcd., 35.6-36.l C. (alcohol) Analysis: Calcd. for CHI-12402:C, 78.42%; H, 9.29%. Found: C, 78.40%; H, 9.39%.

EXAMPLE 'I Isobornyl p-fluorophenyl ether 18 grams camphene and 11.8grams p-fiuorophenol were dissolved in 50 ml. petroleum ether.

The solution was cooled to 5 to 10 C. and

0.5 ml. BF3 (45 per cent solution) was added The reaction mixture waswashed with sodium hydroxide solution and then distilled. The yield was86 per cent of isobornyl p-fluorophenyl ether,

a colorless liquid with a boiling point of 151 C./10 mm.; n =1.5111; d4=1.044; M =71'.25 (Calcd., 70.97)

EXAMPLE 8 Isobornyl p-tert amylphenyl ether 136 grams camphene and 164grams p-tertamylphenol, mixed with 400 ml. benzene-petroleum ether werecooled to 0-10 C. and stirred while 2 ml. of BFa-ether catalyst wasadded during thirty minutes; the mushy solid present dissolved. Ninetyminutes later the reaction mixture was washed with hot 5 per cent NaOHsolution. Distillation yielded 252 "grams (84 per cent yield) ofisobornyl p-tert-amylphenyl ether, B. P.

mainly 199 C./10 mm., a viscous colorless liquid of refractive index n=1.5188 and density d4 =0.9698, which crystallized to a mush onstanding. Recrystallized from alcohol, it had M. P. 48.8-49.2 0.

Analysis: Calcd. for 021E320: C, 83.94%; H, 10.74%. Found: C, 84;15% H,10.91%.-

EXAMPLE 9 Isobornyl 2,4-dichlorophenyl ether 163 grams2,4-dichlorophenol and 136 grams camphene, dissolved in 200 ml.benzene-carbon tetrachloride, were cooled to 0 C. 5 ml. BFsethercatalyst was added to the stirred, cooled mixture during, sixty minutes;solid 2,4-dichloro- .phenol which had crystallized out soon dissolved.

Three hours after the initial catalyst addition the reaction was stoppedby addition of NaOH solution. The reaction mixture yielded 7'7 per centisobornyl 2,4-dichlorophenyl ether, which disstilled as arsomewhatviscous colorless liquid, boiling point 195.5 C/10 mm., n =1.5480, (14:1167 (supercooled liquid), M =8l.45 (Calcd., 70.97), which sooncrystallized to a white solid. Recrystallized from petroleum ether,

M. P. 61.0-61.4 c.

Analysis: Calcd. rorfcmrrzoooizi. c, 64.22%; H, 6.74%; 01, 23.70%.vFound: 0, 63.90%: H, 6.88%; (:1, 23.72%.

EXAMPLE 10 I Isobornyl phenyl ether C./10 millimeters and n =1.5241), 50per cent.

2. p-Isobornylphenol (viscous liquid of boiling point 1'70-181 C./10millimeters and n =1.5453; solidified on standing), 2 per cent. 7 v

The new products may be produced in any convenient manner. Although buttwo halogenated derivatives are mentioned the examples the inventionincludes such compounds regardless of the nature of the halogen, itsposition, or the number of halogen substituents, and whether or not oneor more other substituents are present in the molecule. Condensations ofcamphene or tricyclene with a phenol at'a low temperature will give ahigher yield than at a high temperature.

However, the invention is not limited to products made by any method. Itis defined in the appended claims.v 1

This is a continuation in part of. my application Serial No. 653,426,filed March 9, 1946, now

Patent No. 2,537,636.

What I claim is: 1. Isobornyl aryl ethers of the formula wherein A, B, Cand D are radicals selected from the group consisting" of hydrogen, ahalogen,

alkyl, hydroxyand alkoxy radicals; and R'is iso- 5 6 bomyl, no more thantwo halogen and alkyl UNITED STATES PATENTS groups are present, and'nomore than one alkoxy Number Name Date and y y r ps are P 1A 9 709 Wuytsg 2, 923 Phenyl ether- 2,145,369 Osterhof Jan, 31, 1939 Isobolnyl Cresyl5 2 1 6 132 zi Jam 9 1940 P'WYI ether- 2,213,477 Steinqorf Sept. 3, 1940I o o 2 y ph ether- 2,320,346 Borglin June 1943 Isob r y ,4-d o phe yether- 2 488,489 Borglin NW 1949 LELAND J. KITCHEN.

10 OTHER REFERENCES REFERENCES QITED Martin, Paint Manufacturer, v01. 15(1945),

The following references are of record in the P es 30- 1 file of thispatent:

1. ISOBORNYL ARYL ETHERS OF THE FORMULA